Solar control coatings with quadruple metallic layers

ABSTRACT

A coated article includes a substrate, a first dielectric layer, a first metallic layer, a second dielectric layer, a second metallic layer, a third dielectric layer, a third metallic layer, a fourth dielectric layer, a fourth metallic layer and a fifth dielectric layer. At least one of the metallic layers is a discontinuous metallic layer having discontinuous metallic regions. An optional primer is positioned over any one of the metallic layers. Optionally a protective layer is provided as the outer most layer over the fifth dielectric layer.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/265,878 filed Feb. 1, 2019, which claims priority to U.S. ProvisionalPatent Application No. 62/626,332, filed on Feb. 5, 2018, thedisclosures of which are hereby incorporated by reference in theirentireties.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates generally to solar control coatings with fourmetallic layers.

Technical Considerations

Solar control coatings are known in the fields of architectural andvehicle transparencies. These solar control coatings block or filterselected ranges of electromagnetic radiation, such as in the range ofsolar infrared or solar ultraviolet radiation, to reduce the amount ofsolar energy entering the vehicle or building. This reduction of solarenergy transmittance helps reduce the load on the cooling units of thevehicle or building.

SUMMARY OF THE INVENTION

A coating of the invention includes a coating over at least a portion ofa substrate. The coating includes at least three continuous metalliclayers and at least one discontinuous metallic layer. The discontinuousmetallic layer increases the visible light absorption of the coatingand, in combination with dielectric layers of appropriate thickness, canalso provide the coated article with asymmetrical reflectance.

A coating of the invention includes a coating over at least a portion ofa substrate. The coating includes at least four metallic layersalternating with at least five dielectric layers wherein at least one ofthe metallic layers comprising a discontinuous metallic layer havingdiscontinuous metal regions.

A coated article of the invention includes a substrate and a coatingformed over at least a portion of the substrate. The coating includes afirst dielectric layer formed over at least a portion of the substrate;a first metallic layer formed over at least a portion of the firstdielectric layer; a second dielectric layer formed over at least aportion of the first metallic layer; a second metallic layer formed overat least a portion of the second dielectric layer; a third dielectriclayer formed over at least a portion of the second metallic layer; athird metallic layer formed over at least a portion of the thirddielectric layer; a fourth dielectric layer formed over at least aportion of the third metal layer; a fourth metallic layer formed over atleast a portion of the fourth dielectric layer; a fifth dielectric layerformed over at least a portion of the fourth metallic layer; and anoptional protective layer formed over at least a portion of the thirdmetallic layer. At least one of the metallic layers is a discontinuouslayer. For example, the second metallic layer or the third metalliclayer can be a discontinuous layer.

An additional coated article includes a substrate and a coating stackover at least a portion of the substrate. The coating includes a firstdielectric layer formed over at least a portion of the substrate. Thefirst dielectric layer comprises a first film and a second film over thefirst film. A first metallic layer is positioned over the firstdielectric layer. An optional first primer layer is positioned over thefirst metallic layer. A second dielectric layer is positioned over theoptional first primer layer or the first metallic layer. The seconddielectric layer comprises a first film and a second film over the firstfilm. Optionally a third film is positioned over the second film. Asecond metallic layer is positioned over the second dielectric layer. Athird dielectric layer is positioned over the second metallic layer. Thethird dielectric layer comprises a first film and a second film over thefirst film. Optionally, a third film (of the third dielectric layer) canbe positioned over the second film. A third metallic layer is positionedover the third dielectric layer. A fourth dielectric layer comprisingfirst film and a second film over the first film is positioned over thethird metallic layer. Optionally, a third film (of the fourth dielectriclayer) can be positioned over the second film. A fourth metallic layeris positioned over the fourth dielectric layer. An optional fourthprimer layer is positioned over the fourth metallic layer. A fifthdielectric layer comprising a first film and a second film positionedover the first film is positioned over the fourth metallic layer. Atleast one of the metallic layers is a discontinuous layer havingdiscontinuous metallic regions. For example, the second metallic layeror the third metallic layer is a discontinuous layer havingdiscontinuous metallic regions.

A method of making a coated article including providing a substrate. Afirst dielectric layer is applied over at least a portion of thesubstrate. A first metallic layer is applied over at least a portion ofthe first dielectric layer. An optional first primer layer is appliedover at least a portion of the first metallic layer. A second dielectriclayer is applied over at least a portion of the optional first primerlayer or the first metallic layer. A second metallic layer is appliedover at least a portion of the second dielectric layer. A thirddielectric layer is applied over at least a portion of the optionalsecond primer layer or the second metallic layer. A third metallic layeris applied over at least a portion of the third dielectric layer. Afourth dielectric layer is applied over at least a portion of theoptional third primer layer or the third metallic layer. A fourthmetallic layer is applied over at least a portion of the fourthdielectric layer. A fifth dielectric layer is applied over at least aportion of the optional fourth primer layer or the fourth metalliclayer. At least one of the metallic layers is a discontinuous layerhaving discontinuous metallic regions. For example, the second metalliclayer or the third metallic layer is a subcritical metallic layer havingdiscontinuous metallic regions. The optional primer immediately over thediscontinuous layer can be absent.

Another embodiment of the invention is an architectural transparency.The transparency has a first ply having a number 1 surface and a number2 surface and a second ply having a number 3 surface and a number 4surface. A coating, as described herein, is positioned over at least aportion of the number 2 surface or the number 3 surface.

Another embodiment of the invention is a method of making anarchitectural transparency. The method includes providing a first plyhaving a number 1 surface and a number 2 surface, and a second plyhaving a number 3 surface and a number 4 surface. Either the number 2surface of the first ply or the number 3 surface of the second ply havea coating as described herein. The first ply and the second ply areassembled so that the number 2 surface faces the number three surfaceand that there is a space between the number 2 surface and the number 3surface. The space is filled with a gas.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described with reference to the following drawingfigures wherein like reference numbers identify like parts throughout.

FIG. 1 is a side view (not to scale) of an insulating glass unit (IGU)having a coating of the invention;

FIG. 2 is a side, sectional view (not to scale) of a subcritical metallayer with a primer layer;

FIG. 3 is a side, sectional view (not to scale) of a further coating ofthe invention.

FIG. 4 is a sectional view (not to scale) of a coating of the invention.

FIG. 5 is a sectional view (not to scale) of the coating of theinvention.

FIG. 6 is a sectional view (not to scale) of the coating of theinvention.

FIG. 7 is a sectional view (not to scale) of the coating of theinvention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, spatial or directional terms, such as “left”, “right”,“inner”, “outer”, “above”, “below”, and the like, relate to theinvention as it is shown in the drawing figures. However, it is to beunderstood that the invention can assume various alternativeorientations and, accordingly, such terms are not to be considered aslimiting. Further, as used herein, all numbers expressing dimensions,physical characteristics, processing parameters, quantities ofingredients, reaction conditions, and the like, used in thespecification and claims are to be understood as being modified in allinstances by the term “about”. Accordingly, unless indicated to thecontrary, the numerical values set forth in the following specificationand claims may vary depending upon the desired properties sought to beobtained by the present invention. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical value should at least be construedin light of the number of reported significant digits and by applyingordinary rounding techniques. Moreover, all ranges disclosed herein areto be understood to encompass the beginning and ending range values andany and all subranges subsumed therein. For example, a stated range of“1 to 10” should be considered to include any and all subranges between(and inclusive of) the minimum value of 1 and the maximum value of 10;that is, all subranges beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5,5.5 to 10, and the like. Further, as used herein, the terms “formedover”, “deposited over”, or “provided over” mean formed, deposited, orprovided on but not necessarily in contact with the surface. Forexample, a coating layer “formed over” a substrate does not preclude thepresence of one or more other coating layers or films of the same ordifferent composition located between the formed coating layer and thesubstrate. The terms “visible region” or “visible light” refer toelectromagnetic radiation having a wavelength in the range of 380 nm to800 nm. The terms “infrared region” or “infrared radiation” refer toelectromagnetic radiation having a wavelength in the range of greaterthan 800 nm to 100,000 nm. The terms “ultraviolet region” or“ultraviolet radiation” mean electromagnetic energy having a wavelengthin the range of 300 nm to less than 380 nm. Additionally, all documents,such as, but not limited to, issued patents and patent applications,referred to herein are to be considered to be “incorporated byreference” in their entirety. As used herein, the term “film” refers toa coating region of a desired or selected coating composition. A “layer”can comprise one or more “films”, and a “coating” or “coating stack” cancomprise one or more “layers”. The term “asymmetrical reflectivity”means that the visible light reflectance of the coating from one side isdifferent than that of the coating from the opposite side. The term“critical thickness” means a thickness above which a coating materialforms a continuous, uninterrupted layer and below which the coatingmaterial forms discontinuous regions or islands of the coating materialrather than a continuous layer. The term “subcritical thickness” means athickness below the critical thickness such that the coating materialforms isolated, non-connected regions of the coating material. The term“islanded” means that the coating material is not a continuous layerbut, rather, that the material is deposited to form isolated regions orislands.

For purposes of the following discussion, the invention will bediscussed with reference to use with an architectural transparency, suchas, but not limited to, an insulating glass unit (IGU). As used herein,the term “architectural transparency” refers to any transparency locatedon a building, such as, but not limited to, windows and sky lights.However, it is to be understood that the invention is not limited to usewith such architectural transparencies but could be practiced withtransparencies in any desired field, such as, but not limited to,laminated or non-laminated residential and/or commercial windows,insulating glass units, and/or transparencies for land, air, space,above water and underwater vehicles. Therefore, it is to be understoodthat the specifically disclosed exemplary embodiments are presentedsimply to explain the general concepts of the invention, and that theinvention is not limited to these specific exemplary embodiments.Additionally, while a typical “transparency” can have sufficient visiblelight transmission such that materials can be viewed through thetransparency, in the practice of the invention, the “transparency” neednot be transparent to visible light but may be translucent or opaque.

A non-limiting transparency 10 incorporating features of the inventionis illustrated in FIG. 1 . The transparency 10 can have any desiredvisible light, infrared radiation, or ultraviolet radiation transmissionand/or reflection. For example, the transparency 10 can have a visiblelight transmission of any desired amount, e.g., greater than 0% up to100%.

The exemplary transparency 10 of FIG. 1 is in the form of a conventionalinsulating glass unit and includes a first ply 12 with a first majorsurface 14 (No. 1 surface) and an opposed second major surface 16 (No. 2surface). In the illustrated non-limiting embodiment, the first majorsurface 14 faces the building exterior, i.e., is an outer major surface,and the second major surface 16 faces the interior of the building. Thetransparency 10 also includes a second ply 18 having an outer (first)major surface 20 (No. 3 surface) and an inner (second) major surface 22(No. 4 surface) and spaced from the first ply 12. This numbering of theply surfaces is in keeping with conventional practice in thefenestration art. The first and second plies 12, 18 can be connectedtogether in any suitable manner, such as by being adhesively bonded to aconventional spacer frame 24. A gap or chamber 26 is formed between thetwo plies 12, 18. The chamber 26 can be filled with a selectedatmosphere, such as air, or a non-reactive gas such as argon or kryptongas. A solar control coating 30 (or any of the other coatings describedbelow) is formed over at least a portion of one of the plies 12, 18,such as, but not limited to, over at least a portion of the No. 2surface 16 or at least a portion of the No. 3 surface 20. Although, thecoating could also be on the No. 1 surface or the No. 4 surface, ifdesired. Examples of insulating glass units are found, for example, inU.S. Pat. Nos. 4,193,236; 4,464,874; 5,088,258; and 5,106,663.

In the broad practice of the invention, the plies 12, 18 of thetransparency 10 can be of the same or different materials. The plies 12,18 can include any desired material having any desired characteristics.For example, one or more of the plies 12, 18 can be transparent ortranslucent to visible light. By “transparent” is meant having visiblelight transmission of greater than 0% up to 100%. Alternatively, one ormore of the plies 12, 18 can be translucent. By “translucent” is meantallowing electromagnetic energy (e.g., visible light) to pass throughbut diffusing this energy such that objects on the side opposite theviewer are not clearly visible. Examples of suitable materials include,but are not limited to, plastic substrates (such as acrylic polymers,such as polyacrylates; polyalkylmethacrylates, such aspolymethylmethacrylates, polyethylmethacrylates,polypropylmethacrylates, and the like; polyurethanes; polycarbonates;polyalkylterephthalates, such as polyethyleneterephthalate (PET),polypropyleneterephthalates, polybutyleneterephthalates, and the like;polysiloxane-containing polymers; or copolymers of any monomers forpreparing these, or any mixtures thereof); ceramic substrates; glasssubstrates; or mixtures or combinations of any of the above. Forexample, one or more of the plies 12, 18 can include conventionalsoda-lime-silicate glass, borosilicate glass, or leaded glass. The glasscan be clear glass. By “clear glass” is meant non-tinted or non-coloredglass. Alternatively, the glass can be tinted or otherwise coloredglass. The glass can be annealed or heat-treated glass. As used herein,the term “heat treated” means tempered or at least partially tempered.The glass can be of any type, such as conventional float glass, and canbe of any composition having any optical properties, e.g., any value ofvisible transmission, ultraviolet transmission, infrared transmission,and/or total solar energy transmission. By “float glass” is meant glassformed by a conventional float process in which molten glass isdeposited onto a molten metal bath and controllably cooled to form afloat glass ribbon. Examples of float glass processes are disclosed inU.S. Pat. Nos. 4,466,562 and 4,671,155.

The first and second plies 12, 18 can each be, for example, clear floatglass or can be tinted or colored glass or one ply 12, 18 can be clearglass and the other ply 12, 18 colored glass. Although not limiting tothe invention, examples of glass suitable for the first ply 12 and/orsecond ply 18 are described in U.S. Pat. Nos. 4,746,347; 4,792,536;5,030,593; 5,030,594; 5,240,886; 5,385,872; and 5,393,593. The first andsecond plies 12, 18 can be of any desired dimensions, e.g., length,width, shape, or thickness. In one exemplary automotive transparency,the first and second plies can each be 1 mm to 10 mm thick, such as 1 mmto 8 mm thick, such as 2 mm to 8 mm, such as 3 mm to 7 mm, such as 5 mmto 7 mm, such as 6 mm thick.

The solar control coating 30 of the invention is deposited over at leasta portion of at least one major surface of one of the glass plies 12,18. In the example shown in FIG. 1 , the coating 30 is formed over atleast a portion of the inner surface 16 of the outboard glass ply 12. Asused herein, the term “solar control coating” refers to a coatingcomprised of one or more layers or films that affect the solarproperties of the coated article, such as, but not limited to, theamount of solar radiation, for example, visible, infrared, orultraviolet radiation, reflected from, absorbed by, or passing throughthe coated article; shading coefficient; emissivity, etc. The solarcontrol coating 30 can block, absorb, or filter selected portions of thesolar spectrum, such as, but not limited to, the IR, UV, and/or visiblespectrums.

The solar control coating 30 can be deposited by any conventionalmethod, such as, but not limited to, conventional chemical vapordeposition (CVD) and/or physical vapor deposition (PVD) methods.Examples of CVD processes include spray pyrolysis. Examples of PVDprocesses include electron beam evaporation and vacuum sputtering (suchas magnetron sputter vapor deposition (MSVD)). Other coating methodscould also be used, such as, but not limited to, sol-gel deposition. Inone non-limiting embodiment, the coating 30 can be deposited by MSVD.Examples of MSVD coating devices and methods will be well understood byone of ordinary skill in the art and are described, for example, in U.S.Pat. Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633;4,920,006; 4,938,857; 5,328,768; and 5,492,750.

An exemplary non-limiting solar control coating 30 of the invention isshown in FIG. 4 . This exemplary coating 30 includes a base layer orfirst dielectric layer 440 deposited over at least a portion of a majorsurface of a substrate (e.g., the No. 2 surface 416 of the first ply12). The first dielectric layer 440 can be a single layer or cancomprise more than one film of antireflective materials and/ordielectric materials, such as, but not limited to, metal oxides, oxidesof metal alloys, nitrides, oxynitrides, or mixtures thereof. The firstdielectric layer 440 can be transparent to visible light. Examples ofsuitable metal oxides or metal nitrides for the first dielectric layer440 or any film therein include oxides, nitrides or oxynitrides oftitanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin,aluminum, silicon and mixtures thereof. The metal oxides can have smallamounts of other materials, such as manganese in bismuth oxide, tin inindium oxide, etc. Additionally, oxides of metal alloys or metalmixtures can be used, such as oxides containing zinc and tin (e.g., zincstannate, defined below), oxides of indium-tin alloys, silicon nitrides,silicon aluminum nitrides, or aluminum nitrides. Further, doped metaloxides, such as antimony or indium doped tin oxides or nickel or borondoped silicon oxides, can be used. The first dielectric layer 440 can bea substantially single phase film, such as a metal alloy oxide film,e.g., zinc stannate, or can be a mixture of phases composed of zinc andtin oxides or can be composed of a plurality of films.

As shown in FIG. 5 , the first dielectric layer 440 can comprise amulti-film structure having a first film 442, e.g., a metal alloy oxidefilm, deposited over at least a portion of a substrate (such as theinner major surface 16 of the first ply 12) and a second film 444, e.g.,a metal oxide or oxide mixture film, deposited over the first film 442.In one non-limiting embodiment, the first film 442 can be a zinc/tinalloy oxide. By “zinc/tin alloy oxide” is meant both true alloys andalso mixtures of the oxides. The zinc/tin alloy oxide can be thatobtained from magnetron sputtering vacuum deposition from a cathode ofzinc and tin. One non-limiting cathode can comprise zinc and tin inproportions of 5 wt. % to 95 wt. % zinc and 95 wt. % to 5 wt. % tin,such as 10 wt. % to 90 wt. % zinc and 90 wt. % to 10 wt. % tin. However,other ratios of zinc to tin could also be used. One suitable metal alloyoxide that can be present in the first film 442 is zinc stannate. By“zinc stannate” is meant a composition of Zn_(x)Sn_(1-x)O_(2-x)(Formula 1) where “x” varies in the range of greater than 0 to lessthan 1. For instance, “x” can be greater than 0 and can be any fractionor decimal between greater than 0 to less than 1. For example, wherex=⅔, Formula 1 is Zn_(2/3)Sn_(1/3)O_(4/3), which is more commonlydescribed as “Zn₂SnO₄”. A zinc stannate-containing film has one or moreof the forms of Formula 1 in a predominant amount in the film.

The second film 444 can be a metal oxide film, such as zinc oxide. Thezinc oxide can be deposited from a zinc cathode that includes othermaterials to improve the sputtering characteristics of the cathode. Forexample, the zinc cathode can include a small amount (e.g., up to 20 wt.%, up to 15 wt. %, up to 10 wt. %, or up to 5 wt. %) of tin to improvesputtering. In which case, the resultant zinc oxide film would include asmall percentage of tin oxide, e.g., up to 10 wt. % tin oxide, e.g., upto 5 wt. % tin oxide. A coating layer deposited from a zinc cathodehaving up to 10 wt. % tin (added to enhance the conductivity of thecathode) is referred to herein as “a zinc oxide film” even though asmall amount of tin may be present. The small amount of tin in thecathode (e.g., less than or equal to 10 wt. %, such as less than orequal to 5 wt. %) is believed to form tin oxide in the predominantlyzinc oxide second film 44.

A first metallic layer 446 can be deposited over the first dielectriclayer 440. The first metallic layer 446 can include a reflective metal,such as, but not limited to, metallic gold, copper, palladium, aluminum,silver, or mixtures, alloys, or combinations thereof. In one embodiment,the reflective metal is silver or copper. In another embodiment, thefirst metallic layer 446 has contains silver and copper. The firstmetallic layer 446 can be a continuous layer. Alternatively, the firstmetallic layer 446 can be a discontinuous layer. The first metalliclayer 446 can have a thickness of less than 250 Å, preferable less than200 Å, more preferably less than 125 Å, most preferably less than 100 Å;and/or greater than 50 Å; preferably greater than 60 Å; more preferablygreater than 65 Å; most preferably greater than 70 Å. In one embodiment,the first metallic layer 446 has a thickness of 78 Å to 121 Å. Inanother embodiment, the first metallic layer 446 has a thickness of 70 Åto 99 Å.

An optional first primer layer 448 can be located over the firstmetallic layer 446. The optional first primer layer 448 can be a singlefilm or a multiple film layer. The optional first primer layer 448 caninclude an oxygen-capturing material that can be sacrificial during thedeposition process to prevent degradation or oxidation of the firstmetallic layer 446 during the sputtering process or subsequent heatingprocesses. The optional first primer layer 448 can also absorb at leasta portion of electromagnetic radiation, such as visible light, passingthrough the coating 30. Examples of materials useful for the optionalfirst primer layer 448 include titanium, silicon, silicon dioxide,silicon nitride, silicon oxynitride, nickel-chrome alloys (such asInconel), zirconium, aluminum, alloys of silicon and aluminum, alloyscontaining cobalt and chromium (e.g., Stellite®), and mixtures thereof.For example, the optional first primer layer 448 can be titanium or analloy or mixture of titanium and aluminum.

A second dielectric layer 450 is located over the first metallic layer446 or over the optional first primer layer 448. The second dielectriclayer 450 can comprise one or more metal oxide or metal alloyoxide-containing films, such as those described above with respect tothe first dielectric layer 440. With reference to FIG. 5 , for example,the second dielectric layer 450 can include a first film 452, e.g., azinc oxide film, deposited over first metallic layer 446 or the optionalfirst primer film 448 and a second film 454, e.g., a zinc stannate(Zn₂SnO₄) film, deposited over the first film 452. An optional thirdfilm 456, e.g., a second zinc oxide film, can be deposited over thesecond film.

A second metallic layer 458 is located over the second dielectric layer450 (e.g., over the second zinc oxide film 456, if present, or over thezinc stannate film 454 if not). The metallic material can be metallicgold, copper, palladium, aluminum, silver, or mixtures, alloys, orcombinations thereof. It can be applied as a continuous layer or as adiscontinuous layer such that isolated regions or islands of thematerial are formed rather than a continuous layer of the material. Thesecond metallic layer 458 can have a thickness of that is thicker thanthe first metallic layer 446. The second metallic layer 458 can have athickness that is at least 70 Å, preferably at least 100 Å, morepreferably at least 125 Å, most preferably at least 128 Å; and/or atmost 250 Å, preferably at most 225 Å, more preferably at most 200 Å,most preferably at most 191 Å.

An optional second primer layer 460 can be deposited over the secondmetallic layer 458. The optional second primer layer 460 can be asdescribed above with respect to the optional first primer layer 448. Inone example, the optional second primer layer 460 can be titanium. Anyof the primer layers can be sputtered in a non-reactive atmosphere, sucha low oxygen or oxygen free atmosphere. Then, the coated article couldbe subjected to further processing, such as the deposition of furtheroxide layers in an oxygen containing atmosphere. During this furtherdeposition, the primer would oxidize.

A third dielectric layer 462 can be deposited over the second metalliclayer 458 (e.g., over the optional second primer film 460). The thirddielectric layer 462 can also include one or more metal oxide or metalalloy oxide-containing layers, such as discussed above with respect tothe first and second dielectric layers 440, 450. The third dielectriclayer 462 can include a first film 464, e.g., a zinc oxide film, asecond film 466, e.g., a zinc stannate film deposited over the firstfilm 464. An optional third film 468, e.g., a second zinc oxide layer,can be deposited over the second film.

A third metallic layer 470 is deposited over the third dielectric layer462. The third metallic layer 470 can be of any of the materialsdiscussed above with respect to the first metallic layer 446. In onenon-limiting example, the third metallic layer 470 includes silver,copper, or silver and copper. The third metallic layer 470 is acontinuous layer. Alternatively, the third metallic layer 470 can be adiscontinuous layer. The third metallic layer 470 can be thinner thatthe second metallic layer 458. The third metallic layer can have athickness of at least a thickness of less than 250 Å, preferable lessthan 200 Å, more preferably less than 125 Å, most preferably less than100 Å; and/or greater than 50 Å; preferably greater than 60 Å; morepreferably greater than 65 Å; most preferably greater than 70 Å. In oneembodiment, the first metallic layer 446 has a thickness of 97 Å to 105Å. In another embodiment, the first metallic layer 446 has a thicknessof 70 Å to 125 Å.

An optional third primer layer 472 is located over the third metalliclayer 470. The optional third primer layer 472 can be as described abovewith respect to the optional first or second primer layers 448 or 460.

A fourth dielectric layer 474 is located over the third metallic layer470 (e.g., over the optional third primer layer 472). The fourthdielectric layer 474 can be comprised of one or more metal oxide ormetal alloy oxide-containing layers, such as those discussed above withrespect to the first, second, or third dielectric layers 440, 450, 462.In one non-limiting example, the fourth dielectric layer 474 is amulti-film layer having a first film 476 deposited over the thirdmetallic layer 470 or third primer layer 472, and a second film 478deposited over the first film 476. An optional third film 479 can bedeposited over the second film.

A fourth metallic layer 492 is located over the fourth dielectric layer474. The fourth metallic layer 492 can include a reflective metal, suchas, but not limited to, metallic gold, copper, palladium, aluminum,silver, or mixtures, alloys, or combinations thereof. In one embodiment,the reflective metal is silver, copper or a combination of silver andcopper. In one embodiment, the fourth metallic layer 492 has containssilver and copper. The fourth metallic layer 492 can be a continuouslayer or a discontinuous layer. The fourth metallic layer 492 can bethicker than the first metallic layer 446. The fourth metallic layer 492can also be thicker than the third metallic layer 470. The fourthmetallic layer can have a thickness of at least 100 Å, preferably atleast 150 Å, more preferably at least 175 Å, most preferably at least181 Å; and/or at most 300 Å, preferably at most 275 Å, more preferably250 Å, most preferably at most 240 Å.

An optional fourth primer layer 540 can be deposited over the fourthmetallic layer 492. The fourth primer layer 540 can be as describedabove with respect to the optional first primer layer 448, second primerlayer 460 or third primer layer 472. In one example, the optional fourthprimer layer 540 can be titanium.

A fifth dielectric layer 550 is located over the fourth metallic layer492 (e.g., over the optional fourth primer layer 540). The fifthdielectric layer 550 can be comprised of one or more metal oxide ormetal alloy oxide-containing layers, such as those discussed above withrespect to the first, second, third or fourth dielectric layers 440,450, 462, 474. In one non-limiting example, the fifth dielectric layer550 is a multi-film layer having a first film 502 deposited over thefourth primer layer 540 or fourth metallic layer 492, and a second film504 deposited over the first film 502.

In another non-limiting example, the fifth dielectric layer 550 hasfirst film 502 and a second film 504. The first film comprises zincoxide. The second film comprises silicon nitride.

In another non-limiting example, the fifth dielectric layer 550 has afirst film 502, a second film 504 and a third film (not shown). Thefirst film 502 comprises zinc oxide or zinc stannate. The second film504 comprises zinc stannate, silicon oxide, or silicon oxynitride. Thethird film comprises silicon nitride. Silicon oxide, silicon oxynitridesand silicon nitride can contain aluminum, such as aluminum oxide oraluminum nitride, in amounts of up to 5 weight percent, up to 10 weightpercent, up to 15 weight percent or up to 20 weight percent. In oneembodiment, the second film 504 and the third film are a gradient layerfrom silicon oxide or silicon oxynitrides to silicon nitride.

An optional overcoat 480 can be located over the fifth dielectric layer550. The overcoat 480 can help protect the underlying coating layersfrom mechanical and chemical attack. The optional overcoat 480 can be,for example, a metal oxide or metal nitride layer. For example, theoptional overcoat 480 can be titania, or a mixture of titania andalumina. Other materials useful for the overcoat include other oxides,such as silica, alumina, or a mixture of silica and alumina.

In one non-limiting embodiment, the transparency has a visible lighttransmittance of greater than 20%, such as greater than 30%, such asgreater than 34%. The transparency has a solar heat gain coefficient(SHGC) of less than 0.3, such as less than 0.27, such as less than 0.25,such equal to or as less than 0.22, such as less than 0.20, such as lessthan 0.19; and/or at least 0.10; at least 0.12; at least 0.15; or atleast 0.17. The transparency has a light to solar gain ratio (LSG) of atleast 1.7, at least 1.75, at least 1.8, or at least 1.85; and/or at most2.25; at most 2.15; at most 2.10; or at most 2.06.

Any one of the first metallic layer 446, the second metallic layer 458,the third metallic layer 470 and the fourth metallic layer 492 can be adiscontinuous layer. In one embodiment, only the second metallic layeror only the third metallic layer is a discontinuous layer. In anotherembodiment, only the third metallic layer is the discontinuous layer. Inanother embodiment, only the second metallic layer is the discontinuouslayer.

The coated article can have a total thickness of all the metallic layers(e.g. total thickness being the combine thickness of first, second,third and fourth metallic layers). This total thickness can be in therange of 200 Å to 750 Å, preferably 225 Å to 650 Å, more preferably 250Å to 600 Å, most preferably 252 Å to 582 Å. The coated article can havea total thickness of all of the metallic layers which are continuouslayers (i.e. excluding the thickness of the discontinuous layer(s)). Thetotal thickness of all of the continuous layers can be in the range of150 Å to 750 Å, preferably 200 Å to 650 Å, more preferably 225 Å to 575Å, most preferably 237 Å to 563 Å.

The coated article can have a single discontinuous metallic layerwherein all other metallic layers are continuous metallic layers.

A primer, such as any of the primers described above, may be positionedover and in direct contact with any of the metallic layers. The primermay be a mixture of titanium and aluminum.

The invention further relates to a method of making a coated article. Amethod includes providing a substrate. A first dielectric layer isapplied over at least a portion of the substrate. A first metallic layeris applied over at least a portion of the first dielectric layer. Asecond dielectric layer is applied over at least a portion of the firstmetallic layer. A second metallic layer is applied over at least aportion of the second dielectric layer. A third dielectric layer isapplied over at least a portion of the second metallic layer. A thirdmetallic layer is applied over at least a portion of the thirddielectric layer. A fourth dielectric layer is applied over at least aportion of the fourth metallic layer. A fifth dielectric layer isapplied over at least a portion of the fourth metallic layer. The firstmetallic layer, the second metallic layer, the third metallic layer orthe fourth metallic layer is a discontinuous layer. An optionalprotective overcoat may be applied over the fifth dielectric layer.Optionally, a primer may be applied over the first metallic layer,second metallic layer, third metallic layer and/or fourth metalliclayer. In another embodiment, either the second or third metallic layersis a discontinuous layer.

Another embodiment of the invention is a method of making anarchitectural transparency. The method includes providing a first plyhaving a number 1 surface and a number 2 surface, providing a second plyhaving a number 3 surface and a number 4 surface. Either the number 2surface of the first ply or the number 3 surface of the second ply havethe coating described herein. The first ply and the second ply areassembled in a manner so that the number 2 surface faces the numberthree surface and that there is a space between the number 2 surface andthe number 3 surface. The space is filled with a gas. The gas can be airor argon.

In one embodiment, the discontinuous metallic layer is the thirdmetallic layer. In such an embodiment, the coating can have thicknessfor each layer as described in Table 1, or for each film as described inTable 2. In this embodiment, the third dielectric layer is thicker thanthe first dielectric layer, the second dielectric layer, the fourthdielectric layer and/or the fifth dielectric layer. The third dielectriclayer also comprises the third film.

TABLE 1 Layer Thickness When Discontinuous Metallic layer is the ThirdMetallic layer More Most Range Preferred Preferred Preferred Layer (Å)(Å) (Å) (Å) 1^(st) Dielectric 250-600  300-525 325-475 353-446 1^(st)Metallic 50-300  60-150  70-125 70-99 or 78-121 1^(st) Primer 5-50 15-4520-40 25-36 2^(nd) Dielectric 300-1100  400-1000 475-900 504-824 2^(nd)Metallic 50-300  70-250  75-200  79-191 2^(nd) Primer 5-50 15-45 20-4025-36 3^(rd) Dielectric 75-750 100-600 150-450 199-412 3^(rd) Metallic5-30 10-25 12-22 15-19 3^(rd) Primer 5-50 15-45 17-40 20-36 4^(th)Dielectric 175-800  250-700 300-650 334-603 4^(th) Metallic 50-300 60-275  75-250  80-240 4^(th) Primer 5-50 15-45 20-40 25-36 5^(th)Dielectric 125-550  175-450 225-400 260-340 Overcoat 25-75  30-60 35-5540-50

TABLE 2 Film Thickness When Discontinuous Metallic Layer Is The ThirdMetallic Layer More Most Range Preferred Preferred Preferred Layer (Å)(Å) (Å) (Å) 1^(st) Dielectric: 200-400  225-375 250-350 262-337 1^(st)film 1^(st) Dielectric: 50-200  75-150  90-125  91-109 2^(nd) film1^(st) Metallic 50-300  60-150  70-125 70-99 or 78-121 1^(st) Primer5-50 15-45 20-40 25-36 2^(nd) Dielectric: 25-150  50-125  50-100 63-901^(st) film 2^(nd) Dielectric: 250-800  300-750 350-700 360-680 2^(nd)film 2^(nd) Dielectric: 25-150  50-125  75-100 81-95 3^(rd) film 2^(nd)Metallic 50-300  70-250  75-200  79-191 2^(nd) Primer 5-50 15-45 20-4025-36 3^(rd) Dielectric: 25-200  50-150  75-125  97-105 1^(st) film3^(rd) Dielectric: 50-550  50-450  75-325 100-315 2^(nd) film 3^(rd)Metallic 5-30 10-25 12-22 15-19 3^(rd) Primer 5-50 15-45 17-40 20-364^(th) Dielectric: 150-650  200-550 225-525 246-500 1^(st) film 4^(th)Dielectric: 25-150  50-150  75-125  88-103 2^(nd) film 4^(th) Metallic50-300  60-275  75-250  80-240 4^(th) Primer 5-50 15-45 20-40 25-365^(th) Dielectric: 25-150  50-150  75-125  90-107 1^(st) film 5^(th)Dielectric: 100-400  125-300 150-275 170-250 2^(nd) film Overcoat 25-75 30-60 35-55 40-50

In another embodiment, the discontinuous metallic layer is the secondmetallic layer. In such an embodiment, the coating can have thicknessfor each layer as described in Table 3, or for each film as described inTable 4. In this embodiment, the fourth dielectric layer is thicker thanthe first dielectric layer, the second dielectric layer, the thirddielectric layer and/or the fifth dielectric layer. The fourthdielectric layer also comprises the third film.

TABLE 3 Layer Thickness When The Discontinuous Metallic Layer Is TheSecond Metallic Layer More Most Range Preferred Preferred PreferredLayer (Å) (Å) (Å) (Å) 1^(st) Dielectric 250-600  300-525 325-475 353-4461^(st) Metallic 50-250  75-200 100-175 125-150 1^(st) Primer 5-50 15-4520-40 25-36 2^(nd) Dielectric 225-775  300-650 350-525 400-450 2^(nd)Metallic 5-30 10-25 12-22 15-19 2^(nd) Primer 5-50 15-45 17-40 20-363^(rd) Dielectric 175-600  225-500 260-425 300-350 3^(rd) Metallic50-300  70-250  75-200  79-191 3^(rd) Primer 5-50 15-45 20-40 25-364^(th) Dielectric 350-1125 475-975 615-875 690-785 4^(th) Metallic50-300  60-275  75-250  80-240 4^(th) Primer 5-50 15-45 20-4  25-365^(th) Dielectric 125-550  175-450 225-400 260-340 Overcoat 25-75  30-6035-55 40-50

TABLE 4 Film Thickness When The Discontinuous Metallic Layer Is TheSecond Metallic Layer More Most Range Preferred Preferred PreferredLayer (Å) (Å) (Å) (Å) 1^(st) Dielectric: 200-400  225-375 250-350262-337 1^(st) film 1^(st) Dielectric: 50-200  75-150  90-125  91-1092^(nd) film 1^(st) Metallic 50-250  75-200 100-175 125-150 1^(st) Primer5-50 15-45 20-40 25-36 2^(nd) Dielectric: 25-175  50-150  50-125  75-1001^(st) film 2^(nd) Dielectric: 200-600  250-500 300-400 325-350 2^(nd)film 2^(nd) Metallic 5-30 10-25 12-22 15-19 2^(nd) Primer 5-50 15-4517-40 20-36 3^(rd) Dielectric: 150-400  175-350 200-300 225-250 1^(st)film 3^(rd) Dielectric: 25-200  50-150  60-125  75-100 2^(nd) film3^(rd) Metallic 50-300  70-250  75-200  79-191 3^(rd) Primer 5-50 15-4520-40 25-36 4^(th) Dielectric: 25-175  50-150  75-125  90-110 1^(st)film 4^(th) Dielectric: 300-800  400-700 500-650 550-600 2^(nd) film4^(th) Dielectric: 25-150  25-125  40-100 50-75 3^(rd) film 4^(th)Metallic 50-300  60-275  75-250  80-240 4^(th) Primer 5-50 15-45 20-4025-36 5^(th) Dielectric: 25-150  50-150  75-125  90-107 1^(st) film5^(th) Dielectric: 100-400  125-300 150-275 170-250 2^(nd) film Overcoat25-75  30-60 35-55 40-50

The following Examples illustrate various embodiments of the invention.However, it is to be understood that the invention is not limited tothese specific embodiments.

Examples

Examples 1-4 were prepared by coating glass with the coating stacksdescribed in Table 5.

TABLE 5 Examples 1-4 Example 1 Example 2 Example 3 Example 4 MaterialThickness Thickness Thickness Thickness Glass (Å) (Å) (Å) (Å) Zn₂SnO₄312 301 262 307 ZnO 109 109 91 109 Ag 78 81 121 78 Ti 35 35 35 35 ZnO 6363 71 63 Zn₂SnO₄ 524 551 463 490 ZnO 81 85 95 84 Ag 182 191 128 154 Ti35 36 36 36 ZnO 99 97 105 99 Zn₂SnO₄ 296 315 292 200 Ag 18.8 17.1 15.7517 Zn₂SnO₄ 296 300 246 340 ZnO 103 102 88 103 Ag 188 197 240 181 Ti 2828 28 28 ZnO 90 90 107 90 Zn₂SnO₄ 172 170 205 170 TiO₂ 44 44 44 44

In Example 1, the LTA was 34.0, the SHGC was 0.183 and the LSG was 1.86.In Example 2, the LTA was 34.3, the SHGC was 0.178 and the LSG was 1.93.In Example 3, the LTA was 37.3, the SHGC was 0.182 and the LSG was 2.05.In Example 4, the LTA was 40.1, the SHGC was 0.22, and the LSG was 1.82.

Examples 5-7 were prepared by coating glass with the coating stacksdescribed in Table 6.

TABLE 6 Examples 5-7 Example 5 Example 6 Example 7 Material ThicknessThickness Thickness Glass (nm) (nm) (nm) Zn₂SnO₄ 30.7 33.7 31.7 ZnO 10.910.9 10.9 Ag 11.2 10.7 10.7 Ti 3.5 3.5 3.5 ZnO 6.3 6.3 6.3 Zn₂SnO₄ 42.036.0 68.0 ZnO 8.1 8.1 8.1 Ag 12.4 7.9 16.4 Ti 3.6 3.6 3.6 ZnO 9.9 9.99.9 Zn₂SnO₄ 20.0 10.0 20.0 Ag 1.5 1.9 1.7 Ti 2.0 3.0 3.5 Zn₂SnO₄ 34.050.0 35.0 ZnO 10.3 10.3 10.3 Ag 23.8 19.5 10.0 Ti 2.8 2.8 2.8

Example 8 was prepared by coating glass with the coating stack describedin Table 7.

TABLE 7 Example 8 Material Example 8 Glass Thickness (nm) Zn₂SnO₄ 31.7ZnO 10.9 Ag 13.2 Ti 3.5 ZnO 9.0 Zn₂SnO₄ 33.0 Ag 1.7 Zn₂SnO₄ 24.0 ZnO 8.0Ag 16.4 Ti 3.6 ZnO 9.9 Zn₂SnO₄ 57.0 ZnO 5.4 Ag 8.0 Ti 2.8 ZnO 9.0Zn₂SnO₄ 21.0 TiO₂ 4.4

The invention is further described in the following numbered clauses.

Clause 1: A coated article comprising: a substrate; a first dielectriclayer over at least a portion of the substrate; a first metallic layerover at least a portion of the first dielectric layer; an optional firstprimer over at least a portion of the first metallic layer; a seconddielectric layer over at least a portion of the first primer layer; asecond metallic layer over at least a portion of the second dielectriclayer; an optional second primer over at least a portion of the secondmetallic layer; a third dielectric layer over at least a portion of thesecond primer layer; a third metallic layer over at least a portion ofthe third dielectric layer; an optional third primer over at least aportion of the third metallic layer; a fourth dielectric layer over atleast a portion of the third primer layer; a fourth metallic layer overat least a portion of the fourth dielectric layer; and an optionalfourth primer over at least a portion of the fourth metallic layer; afifth dielectric layer over at least a portion of the fourth metalliclayer; wherein the first metallic layer, the second metallic layer, thethird metallic layer or the fourth metallic layer is a discontinuouslayer.

Clause 2: The article of clause 1 wherein the optional first primer, thesecond primer, the optional third primer or the optional fourth primeris selected from titanium, silicon-aluminum alloys, nickel alloys,alloys containing nickel and chromium, cobalt alloys, alloys containingcobalt and chromium, copper, aluminum, silicon, nickel-chromium alloy,zirconium, mixtures thereof, and alloys thereof.

Clause 3: The article of clause 1 or 2 wherein the optional firstprimer, the optional second primer, the optional third primer or thefourth primer is deposited as a metal and subsequently oxidized.

Clause 4: The article of any of the clauses 1-3, wherein thediscontinuous layer comprises silver or copper.

Clause 5: The article of any of the clauses 1-4, wherein thediscontinuous layer comprises silver and copper.

Clause 6: The article of any of the clauses 1-5, wherein the seconddielectric layer, or the third dielectric layer comprises a zinc oxidelayer, and a zinc stannate layer over the zinc oxide layer.

Clause 7: The article of any of the clauses 1-6 further comprising aprotective coating over the fifth dielectric layer.

Clause 8: The article of any of the clauses 1-7 wherein the firstdielectric layer, includes an oxide, nitride or oxynitrides of titanium,hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum,silicon or a mixture thereof.

Clause 9: The article of any of the clauses 1-8 wherein the seconddielectric layer, includes an oxide, nitride or oxynitride of titanium,hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum,silicon or a mixture thereof.

Clause 10: The article of any of the clauses 1-9 wherein the thirddielectric layer, includes an oxide, nitride or oxynitride of titanium,hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum,silicon or a mixture thereof.

Clause 11: The article of any of the clauses 1-10 wherein the fourthdielectric layer, includes an oxide, nitride or oxynitride of titanium,hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum,silicon or a mixture thereof.

Clause 12: The article of any of the clauses 1-11 wherein the fifthdielectric layer, includes an oxide, nitride or oxynitride of titanium,hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon,aluminum or a mixture thereof.

Clause 13: The article of any of the clauses 1-12 wherein the firstdielectric layer, the second dielectric layer, the third dielectriclayer and/or the fourth dielectric layer includes zinc oxide.

Clause 14: The article of any of the clauses 1-13 wherein the firstdielectric layer, the second dielectric layer, the third dielectriclayer and/or the fourth dielectric layer includes zinc stannate.

Clause 15: The article of any of the clauses 1-14 wherein the fifthdielectric layer includes zinc oxide or zinc stannate.

Clause 16: The article of any of the clauses 1-15 wherein the fifthdielectric layer includes silicon oxide, silicon nitride, siliconoxynitrides or a mixture thereof.

Clause 17: The article of any of the clauses 1-16 wherein the firstdielectric layer includes a first film including zinc stannate over thesubstrate, and a second film including zinc oxide over the first film.

Clause 18: The article of any of the clauses 1-17 wherein the seconddielectric layer includes a first film including zinc oxide, and asecond film including zinc stannate.

Clause 19: The article of any of the clauses 1-18 wherein the thirddielectric layer includes a first film including zinc oxide a secondfilm including zinc stannate and an optional third film including zincoxide.

Clause 20: The article of any of the clauses 1-19 wherein the fourthdielectric layer includes a first film of zinc stannate and a secondfilm of zinc oxide.

Clause 21: The article of any of the clauses of 1-20 wherein the fifthdielectric layer includes a first film including zinc oxide or zincstannate.

Clause 22: The article of any of the clauses 1-21 wherein the fifthdielectric layer further includes a second film including silicon oxide,silicon oxynitride, silicon nitride or a mixture thereof.

Clause 23: The article of clause 22 wherein the second film is agradient layer of silicon oxide to silicon nitride.

Clause 24: The article of clause 22 wherein the second film is agradient layer of silicon oxynitride to silicon nitride.

Clause 25: The article of any of the clauses 1-24 wherein the firstmetallic film includes metallic gold, copper, palladium, aluminum,silver, or mixtures, alloys, or combinations thereof.

Clause 26: The article of any of the clauses 1-25 wherein the secondmetallic film includes metallic gold, copper, palladium, aluminum,silver, or mixtures, alloys, or combinations thereof.

Clause 27: The article of any of the clauses 1-26 wherein the thirdmetallic film includes metallic gold, copper, palladium, aluminum,silver, or mixtures, alloys, or combinations thereof.

Clause 28: The article of any of the clauses 1-27 wherein the fourthmetallic film includes metallic gold, copper, palladium, aluminum,silver, or mixtures, alloys, or combinations thereof.

Clause 29: The article of any of the clauses 1-28 wherein the firstmetallic film includes copper, silver, or a mixture thereof.

Clause 30: The article of any of the clauses 1-29 wherein the secondmetallic film includes copper, silver, or a mixture thereof.

Clause 31: The article of any of the clauses 1-30 wherein the thirdmetallic film includes copper, silver, or a mixture thereof.

Clause 32: The article of any of the clauses 1-31 wherein the fourthmetallic film includes copper, silver, or a mixture thereof.

Clause 33: The article of any of the clauses 1-34 wherein the firstprimer, the second primer, the third primer and/or the fourth primerincludes titanium, aluminum, or a mixture thereof, wherein the primer isdeposited as a metal and at least partially oxidized by the depositionof the next layer over the primer.

Clause 34: The article of any of the clauses 1-33 wherein the secondmetallic layer or the third metallic layer is a discontinuous layer.

Clause 35: The article of clause 34 wherein the discontinuous layer hasa thickness of at most 36 Å, preferably at most 26 Å; more preferably atmost 20 Å; most preferably at most 19 Å; and at least 5 Å; preferably atleast 7 Å; more preferably at least 10 Å; most preferably at least 15 Å.

Clause 36: The article of clauses 34 or 35 wherein the second metalliclayer is the discontinuous layer.

Clause 37: The article of clauses 34 or 35 wherein the third metalliclayer is the discontinuous layer.

Clause 38: The article of clauses 34, 35, 36 or 37 wherein at least twoof the metallic layer are continuous metallic layers.

Clause 39: The article of clauses 34, 35 or 36 wherein the firstmetallic layer and the fourth metallic layer are continuous metalliclayers, wherein the first metallic layer has a thickness of less than250 Å, preferable less than 200 Å, more preferably less than 125 Å, mostpreferably less than 100 Å; and/or greater than 50 Å; preferably greaterthan 60 Å; more preferably greater than 65 Å; most preferably greaterthan 70 Å; and wherein the fourth metallic layer has a thickness of atleast 100 Å, preferably at least 150 Å, more preferably at least 175 Å,most preferably at least 181 Å; and/or at most 300 Å, preferably at most275 Å, more preferably 250 Å, most preferably at most 240 Å.

Clause 40: The article of clauses 34, 35 or 36 wherein three of themetallic layers are continuous metallic layers.

Clause 41: The article of clause 40 wherein the continuous metalliclayers are the first metallic layer, the second metallic layer and thefourth metallic layer wherein the first metallic layer has a thicknessof less than 250 Å, preferable less than 200 Å, more preferably lessthan 125 Å, most preferably less than 100 Å; and/or greater than 50 Å;preferably greater than 60 Å; more preferably greater than 65 Å; mostpreferably greater than 70 Å; wherein the fourth metallic layer has athickness of at least 100 Å, preferably at least 150 Å, more preferablyat least 175 Å, most preferably at least 181 Å; and/or at most 300 Å,preferably at most 275 Å, more preferably 250 Å, most preferably at most240 Å; and wherein the second metallic layer has a thickness that is atleast 70 Å, preferably at least 100 Å, more preferably at least 125 Å,most preferably at least 128 Å; and/or at most 250 Å, preferably at most225 Å, more preferably at most 200 Å, most preferably at most 191 Å.

Clause 42: The article of clause 40 wherein the continuous metalliclayers are the first metallic layer, the third metallic layer and thefourth metallic layer wherein the first metallic layer has a thicknessof less than 250 Å, preferable less than 200 Å, more preferably lessthan 125 Å, most preferably less than 100 Å; and/or greater than 50 Å;preferably greater than 60 Å; more preferably greater than 65 Å; mostpreferably greater than 70 Å; and wherein the fourth metallic layer hasa thickness of at least 100 Å, preferably at least 150 Å, morepreferably at least 175 Å, most preferably at least 181 Å; and/or atmost 300 Å, preferably at most 275 Å, more preferably 250 Å, mostpreferably at most 240 Å.

Clause 43: The article of any of the clauses 34-42 wherein thecontinuous metallic layer has a thickness in the range of 50 Å to 300 Å,preferably 60 Å to 250 Å, more preferably 65 Å to 225 Å, most preferablybetween 71 Å to 205 Å.

Clause 44: The article of any of the clauses 1-43 wherein the articlehas a LTA between 30 and 45, preferably between 32 and 43; morepreferably between 33 and 43; most preferably between 34 and 41.

Clause 45: The article of any of the clauses 1-44 wherein the articlehas a SHGC of between 0.170 and 0.200, preferably between 0.174 and0.250; more preferably between 0.175 and 0.230; most preferably between0.178 and 0.220.

Clause 46: The article of any of the clauses 1-45 wherein the articlehas a LSG between 1.50 and 2.50; preferably between 1.70 and 2.25; morepreferably between 1.75 and 2.15; most preferably between 1.82 and 2.05.

Clause 47: A coated article having a substrate; a first dielectric film;a second dielectric film over the first dielectric film; a firstmetallic film over the second dielectric film comprising silver; a thirddielectric film over the first metallic film; a fourth dielectric filmover the third dielectric film; a second metallic layer over the fourthdielectric film wherein the second metallic film comprises silver; afifth dielectric film over the second metallic film; a sixth dielectricfilm over the fifth dielectric film; a third metallic layer over thesixth dielectric film wherein the third metallic film comprises silver;a seventh dielectric film over the third metallic film; an eighthdielectric film over the seventh dielectric film; a fourth metallic filmover the eighth dielectric film wherein the fourth metallic filmcomprises silver; and a ninth dielectric film over the fourth metallicfilm; wherein the first metallic film, the second metallic film, thethird metallic film or the fourth metallic film is a discontinuous film.

Clause 48: The coated article of clause 47 wherein the first dielectricfilm includes zinc stannate.

Clause 49: The coated article of any of the clauses 47-48 wherein aplurality of primers is positioned over and in direct contact with eachmetallic film.

Clause 51: The coated article of any of the clauses 47-50, wherein thesecond metallic film is the discontinuous layer.

Clause 52: The coated article of any of the clauses 47-50, wherein thethird metallic film is the discontinuous layer.

Clause 53: The coated article of any of the clauses 47-52, wherein atleast two of the metallic films are continuous layers.

Clause 54: The coated article of any of the clauses 47-52 wherein atleast three of the metallic films are continuous layers.

Clause 55: The coated article of any of the clauses 47-54 furthercomprising a protective layer over the ninth dielectric film.

Clause 56: The article of any of the clauses 47-55 wherein the articlehas a LTA between 30 and 45, preferably between 32 and 43; morepreferably between 33 and 43; most preferably between 34 and 41.

Clause 57: The article of any of the clauses 47-56 wherein the articlehas a SHGC of between 0.170 and 0.200, preferably between 0.174 and0.250; more preferably between 0.175 and 0.230; most preferably between0.178 and 0.220.

Clause 58: The article of any of the clauses 47-57 wherein the articlehas a LSG between 1.50 and 2.50; preferably between 1.70 and 2.25; morepreferably between 1.75 and 2.15; most preferably between 1.82 and 2.05.

Clause 59: A method of making a coated article comprising providing asubstrate, applying a first dielectric layer over at least a portion ofthe substrate, applying a first metallic layer over at least a portionof the first dielectric layer, applying a second dielectric layer overat least a portion of the first metallic layer, applying a secondmetallic layer over at least a portion of the second dielectric layer,applying a third dielectric layer over at least a portion of the secondmetallic layer, applying a third metallic layer over at least a portionof the third dielectric layer, applying a fourth dielectric layer overat least a portion of the fourth metallic layer, applying a fifthdielectric layer over at least a portion of the fourth metallic layer;wherein the first metallic layer, the second metallic layer, the thirdmetallic layer or the fourth metallic layer is a discontinuous layer.

Clause 60: The method of clause 59 further comprising applying aprotective over coat over at least a portion of the fifth dielectriclayer.

Clause 61: The method of clause 59 or 60 further comprising applying aprimer layer over at least a portion of the first metallic layer, thesecond metallic layer, the third metallic layer and/or the fourthmetallic layer, wherein the primer layer is applied as a metal andsubsequently oxidized upon the application of the next layer.

Clause 62: The method of any of the clauses 59-61 wherein at least thefirst metallic layer is a continuous metallic layer.

Clause 63: The method of any of the clauses 59-62 wherein at least thefourth metallic layer is a continuous metallic layer.

Clause 64: The method of any of the clauses 59-63 wherein the thirdmetallic layer is a discontinuous metallic layer.

Clause 65: The method of any of the clauses—59-63 wherein the secondmetallic layer is a discontinuous metallic layer.

Clause 66: An architectural transparency comprising a first ply having anumber 1 surface and a number 2 surface, a second ply having a number 3surface and a number 4 surface, and a coating position over at least aportion of the number 2 surface or the number 3 surface, wherein thecoating comprises the coating provided in any of the clauses 1-58.

Clause 67: The architectural transparency according to clause 66 furthercomprising a space between the number 2 surface and the number 3 surfacewherein the space is filled with a gas.

Clause 68: The architectural transparency according to clause 67 whereinthe gas is argon.

Clause 69: The architectural transparency according to any of theclauses 66-68 wherein the number 1 surface is configured to face towardsthe outside of a structure where the architectural transparency isinstalled.

Clause 70: The architectural transparency according to any of theclauses 66-69 wherein the number 4 surface is configured to face towardsthe interior of a structure where the architectural transparency is tobe installed.

Clause 71: A method of making an architectural transparency comprisingproviding a first ply having a number 1 surface and a number 2 surface,providing a second ply having a number 3 surface and a number 4 surface,wherein either the number 2 surface of the first ply or the number 3surface of the second ply comprises a coating as provided in any of theclauses 1-58; assembling the first ply and the second ply in a manner sothat the number 2 surface faces the number three surface and that thereis a space between the number 2 surface and the number 3 surface whereinthe space is filled with a gas.

Clause 72: The method of clause 71 wherein the gas is argon.

It will be readily appreciated by those skilled in the art thatmodifications may be made to the invention without departing from theconcepts disclosed in the foregoing description. Accordingly, theparticular embodiments described in detail herein are illustrative onlyand are not limiting to the scope of the invention, which is to be giventhe full breadth of the appended claims and any and all equivalentsthereof.

What is claimed is:
 1. A coated article comprising: a substrate; a firstdielectric layer comprising zinc and having a thickness in the range of353 Å to 446 Å over at least a portion of the substrate; a firstmetallic layer comprising silver and having a thickness in the range of75 Å to 200 Å over at least a portion of the first dielectric layer; afirst primer layer having a thickness in the range of 25 Å to 36 Å overat least a portion of the first metallic layer; a second dielectriclayer comprising zinc and having a thickness in the range of 350 Å to775 Å over at least a portion of the first primer layer; a secondmetallic layer over at least a portion of the second dielectric layer; asecond primer layer having a thickness in the range of 20 Å to 36 Å overat least a portion of the second metallic layer; a third dielectriclayer comprising zinc and having a thickness in the range of 260 Å to425 Å over at least a portion of the second primer layer; a thirdmetallic layer comprising silver and having a thickness in the range of70 Å to 250 Å over at least a portion of the third dielectric layer; athird primer layer having a thickness in the range of 25 Å to 36 Å overat least a portion of the third metallic layer; a fourth dielectriclayer comprising zinc and having a thickness in the range of 350 Å to785 Å over at least a portion of the third primer layer; a fourthmetallic layer comprising silver and having a thickness in the range of80 Å to 240 Å over at least a portion of the fourth dielectric layer; afourth primer layer having a thickness in the range of 25 Å to 36 Å overat least a portion of the fourth metallic layer; a fifth dielectriclayer comprising zinc and having a thickness in the range of 125 Å to340 Å over at least a portion of the fourth primer layer; and anovercoat comprising titanium and having a thickness in the range of 25 Åto 75 Å over at least a portion of the fifth dielectric layer, whereinthe second metallic layer is a discontinuous layer comprising silver andhaving a thickness in the range of 12 Å to 22 Å, wherein the firstmetallic layer, the third metallic layer, and the fourth metallic layerare continuous metallic layers, wherein the total thickness of all ofthe continuous metallic layers is in the range of 225 Å to 650 Å,wherein the article comprises a solar heat gain coefficient (“SHGC”) ofless than 0.20, and wherein the article comprises a visible lighttransmittance (“LTA”) of between 34% and 45%.
 2. The article of claim 1,wherein the first primer is selected from titanium, silicon-aluminumalloys, nickel alloys, alloys containing nickel and chromium, cobaltalloys, alloys containing cobalt and chromium, copper, aluminum,silicon, nickel-chromium alloy, zirconium, mixtures thereof, and alloysthereof.
 3. The article of claim 2, wherein the first primer layer isdeposited as a metal and subsequently oxidized.
 4. The article of claim1, wherein the second dielectric layer comprises a zinc oxide layer, anda zinc stannate layer over the zinc oxide layer.
 5. The article of claim1, wherein the third dielectric layer comprises a zinc stannate layer,and a zin oxide layer over the zinc stannate layer.
 6. The article ofclaim 1, wherein the second metallic layer has a thickness in the rangeof 15 Å to 19 Å.
 7. The article of claim 1, wherein the articlecomprises only one discontinuous layer.
 8. The article of claim 1,comprising a LSG between 1.50 and 2.50.
 9. The article of claim 1,wherein the first metallic layer has a thickness in the range of from125 Å to 150 Å.
 10. The article of claim 1, wherein the seconddielectric layer has a thickness in the range of from 400 Å to 450 Å.11. The article of claim 1, wherein at least one of the first dielectriclayer, the second dielectric layer, the third dielectric layer, thefourth dielectric layer, and the fifth dielectric layer comprises zincaluminum.
 12. The article of claim 1, wherein at least one of the firstprimer layer, the second primer layer, the third primer layer, and thefourth primer layer comprises aluminum.
 13. The article of claim 1,wherein the substrate comprises glass.
 14. An architectural transparencycomprising: a first ply having a number 1 surface and a number 2surface; a second ply having a number 3 surface and a number 4 surface;and a coating position over at least a portion of the number 2 surfaceor the number 3 surface, wherein the coating comprises: a firstdielectric layer comprising zinc and having a thickness in the range of353 Å to 446 Å; a first metallic layer comprising silver and having athickness in the range of 75 Å to 200 Å over at least a portion of thefirst dielectric layer; a first primer layer having a thickness in therange of 25 Å to 36 Å over at least a portion of the first metalliclayer; a second dielectric layer comprising zinc and having a thicknessin the range of 350 Å to 775 Å over at least a portion of the firstprimer layer; a second metallic layer over at least a portion of thesecond dielectric layer; a second primer layer having a thickness in therange of 20 Å to 36 Å over at least a portion of the second metalliclayer; a third dielectric layer comprising zinc and having a thicknessin the range of 260 Å to 425 Å over at least a portion of the secondprimer layer; a third metallic layer comprising silver and having athickness in the range of 70 Å to 250 Å over at least a portion of thethird dielectric layer; a third primer layer having a thickness in therange of 25 Å to 36 Å over at least a portion of the third metalliclayer; a fourth dielectric layer comprising zinc and having a thicknessin the range of 350 Å to 785 Å over at least a portion of the thirdprimer layer; a fourth metallic layer comprising silver and having athickness in the range of 80 Å to 240 Å over at least a portion of thefourth dielectric layer; a fourth primer layer having a thickness in therange of 25 Å to 36 Å over at least a portion of the fourth metalliclayer; a fifth dielectric layer comprising zinc and having a thicknessin the range of 125 Å to 340 Å over at least a portion of the fourthprimer layer; and an overcoat comprising titanium and having a thicknessin the range of 25 Å to 75 Å over at least a portion of the fifthdielectric layer, wherein the second metallic layer is a discontinuouslayer comprising silver and having a thickness in the range of 12 Å to22 Å, wherein the first metallic layer, the third metallic layer, andthe fourth metallic layer are continuous metallic layers, wherein thetotal thickness of all of the continuous metallic layers is in the rangeof 225 Å to 650 Å, wherein the transparency comprises a solar heat gaincoefficient (“SHGC”) of less than 0.20, and wherein the transparencycomprises a visible light transmittance (“LTA”) of between 34% and 45%.15. The transparency of claim 14, comprising a LSG between 1.50 and2.50.
 16. The transparency of claim 14, wherein the second metalliclayer has a thickness in the range of 15 Å to 19 Å.
 17. The transparencyof claim 14, wherein at least one of the first dielectric layer, thesecond dielectric layer, the third dielectric layer, the fourthdielectric layer, and the fifth dielectric layer comprises zincaluminum.
 18. The transparency of claim 14, wherein at least one of thefirst primer layer, the second primer layer, and the third primer layercomprises aluminum.
 19. The transparency of claim 14, wherein the seconddielectric layer comprises a zinc oxide layer, and a zinc stannate layerover the zinc oxide layer.
 20. A method of making a coated articlecomprising the steps of: providing a substrate; applying a firstdielectric layer comprising zinc and having a thickness in the range of353 Å to 446 Å over at least a portion of the substrate; applying afirst metallic layer comprising silver and having a thickness in therange of 75 Å to 200 Å over at least a portion of the first dielectriclayer; applying a first primer layer having a thickness in the range of25 Å to 36 Å over at least a portion of the first metallic layer;applying a second dielectric layer comprising zinc and having athickness in the range of 350 Å to 775 Å over at least a portion of thefirst primer layer; applying a second metallic layer over at least aportion of the second dielectric layer; applying a second primer layerhaving a thickness in the range of 20 Å to 36 Å over at least a portionof the second metallic layer; applying a third dielectric layercomprising zinc and having a thickness in the range of 260 Å to 425 Åover at least a portion of the second primer layer; applying a thirdmetallic layer comprising silver and having a thickness in the range of70 Å to 250 Å over at least a portion of the third dielectric layer;applying a third primer layer having a thickness in the range of 25 Å to36 Å over at least a portion of the third metallic layer; applying afourth dielectric layer comprising zinc and having a thickness in therange of 350 Å to 785 Å over at least a portion of the third primerlayer; applying a fourth metallic layer comprising silver and having athickness in the range of 80 Å to 240 Å over at least a portion of thefourth dielectric layer; applying a fourth primer layer having athickness in the range of 25 Å to 36 Å over at least a portion of thefourth metallic layer; applying a fifth dielectric layer comprising zincand having a thickness in the range of 125 Å to 340 Å over at least aportion of the fourth primer layer; and applying an overcoat comprisingtitanium and having a thickness in the range of 25 Å to 75 Å over atleast a portion of the fifth dielectric layer, wherein the secondmetallic layer is a discontinuous layer comprising silver and having athickness in the range of 12 Å to 22 Å, wherein the first metalliclayer, the second metallic layer, and the fourth metallic layer arecontinuous metallic layers; wherein the total thickness of all of thecontinuous metallic layers is within the range of 225 Å to 650 Å;wherein the article comprises a solar heat gain coefficient (“SHGC”) ofless than 0.20; and wherein the article comprises a visible lighttransmittance (“LTA”) of between 34% and 45%.